Search results for: non equilibrium thermodynamics

Authors: Nicolas Giraudo, Peter Thissen

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In this paper we bring up new aspects of the metal proton exchange reaction (MPER, also called early stage hydration): (1) its dependence of the number of protons consumed by the preferential exchanged cations on the pH value applied at the water/wollastonite interface and (2) strong anisotropic characteristics detected in atomic force microscopy (AFM) and low energy ion scattering spectroscopy measurements (LEIS). First we apply density functional theory (DFT) calculations to compare the kinetics of the reaction on different wollastonite surfaces, and combine it with ab initio thermodynamics to set up a model describing (1) the release of Ca in exchange with H coming from the water/wollastonite interface, (2) the dependence of the MPER on the chemical potential of protons. In the second part of the paper we carried out in-situ AFM and inductive coupled plasma atomic emission spectroscopy (ICP-OES) measurements in order to evaluate the predicted values. While a good agreement is found in the basic and neutral regime (pH values from 14-4), an increasing mismatch appears in the acidic regime (pH value lower 4). This is finally explained by non-equilibrium etching, dominating over the MPER in the very acidic regime.

Keywords: anisotropy, calcium silicate, cement, density functional theory, hydration

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Authors: Abhishek Kumar, Nilam

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As we know that, time delay exists almost in every biological phenomenon. Therefore, in the present study, we propose a susceptible–infected–recovered (SIR) epidemic model along with time delay, modulated incidence rate of infection, and Holling Type II nonlinear treatment rate. The present model aims to provide a strategy to control the spread of epidemics. In the mathematical study of the model, it has been shown that the model has two equilibriums which are named as disease-free equilibrium (DFE) and endemic equilibrium (EE). Further, stability analysis of the model is discussed. To prove the stability of the model at DFE, we derived basic reproduction number, denoted by (R₀). With the help of basic reproduction number (R₀), we showed that the model is locally asymptotically stable at DFE when the basic reproduction number (R₀) less than unity and unstable when the basic reproduction number (R₀) is greater than unity. Furthermore, stability analysis of the model at endemic equilibrium has also been discussed. Finally, numerical simulations have been done using MATLAB 2012b to exemplify the theoretical results.

Keywords: time delayed SIR epidemic model, modulated incidence rate, Holling type II nonlinear treatment rate, stability

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Authors: N. Bourayou, A. -H. Meniai, A. Gouaoura

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The presence of salt can either raise or lower the distribution coefficient of a solute acetic acid in liquid- liquid equilibria. The coefficient of solute is defined as the ratio of the composition of solute in solvent rich phase to the composition of solute in diluents (water) rich phase. The phenomena are known as salting–out or salting-in, respectively. The effect of monovalent salt, sodium chloride and the bivalent salt, sodium sulfate on the distribution of acetic acid between 1-butanol and water at 298.15K were experimentally shown to be effective in modifying the liquid-liquid equilibrium of water/acetic acid/1-butanol system in favour of the solvent extraction of acetic acid from an aqueous solution with 1-butanol, particularly at high salt concentrations of both salts. All the two salts studied are found to have to salt out effect for acetic acid in varying degrees. The experimentally measured data were well correlated by Eisen-Joffe equation. NRTL model for solvent mixtures containing salts was able to provide good correlation of the present liquid-liquid equilibrium data. Using the regressed salt concentration coefficients for the salt-solvent interaction parameters and the solvent-solvent interaction parameters obtained from the same system without salt. The calculated phase equilibrium was in a quite good agreement with the experimental data, showing the ability of NRTL model to correlate salt effect on the liquid-liquid equilibrium.

Keywords: activity coefficient, Eisen-Joffe, NRTL model, sodium chloride

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Authors: Aidaoui Ahleme, Hasseine Abdelmalek

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Acetic acid is one of the simplest and most widely used carboxylic acids having many important chemical and industrial applications. Total worldwide production of acetic acid is about 6.5 million tonnes per year. A great deal of efforts has been made in developing feasible and economic method for recovery of carboxylic acids. Among them, Liquid-liquid extraction using aqueous two-phase systems (ATPS) has been demonstrated to be a highly efficient separation technique. The study of efficiently separating and recovering Acetic acid from aqueous solutions is an important significance on industry and environmentally sustainable development. Many research groups in different countries are working in this field and some methods are proposed in the literature. In this work, effect of sodium chloride with different content (5%, 10% and 20%) on the liquid-liquid equilibrium data of (water+ acetic acid+ DCM) system is investigated. The addition of the salt in an aqueous solution introduces ionic forces which affect liquid-liquid equilibrium and which influence directly the distribution coefficient of the solute. From the experimental results, it can be concluded that when the percentage of salt increases in the aqueous solution, the equilibrium between phases is modified in favor of the extracted phase.

Keywords: acetic acid recovery, aqueous solution, salting-effect, sodium chloride

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Authors: Ammar Alsabery, Habibis Saleh, Norazam Arbin, Ishak Hashim

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Unsteady natural convection and heat transfer in a square cavity partially filled with porous media using a thermal non-equilibrium model is studied in this paper. The left vertical wall is maintained at a constant hot temperature and the right vertical wall is maintained at a constant cold temperature, while the horizontal walls are adiabatic. The governing equations are obtained by applying the Darcy model and Boussinesq approximation. COMSOL's finite element method is used to solve the non-dimensional governing equations together with specified boundary conditions. The governing parameters of this study are the Rayleigh number, the modified thermal conductivity ratio, the inter-phase heat transfer coefficien and the time independent. The results presented for values of the governing parameters in terms of streamlines in both fluid/porous layer, isotherms of fluid and solid porous layer, isotherms of fluid layer, and average Nusselt number.

Keywords: unsteady natural convection, thermal non-equilibrium model, Darcy model

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Authors: Ahmadali Shirazytabar, Hamidreza Namazi

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The inherent irreversibility of thermo-acoustics primarily in the stack region causes poor efficiency of thermo-acoustic engines which is the major weakness of these devices. In view of the above, this study examines entropy generation in the stack of a thermo-acoustic system. For this purpose two parallel plates representative of the stack is considered. A general equation for entropy generation is derived based on the Second Law of thermodynamics. Assumptions such as Rott’s linear thermo-acoustic approximation, boundary layer type flow, etc. are made to simplify the governing continuity, momentum and energy equations to achieve analytical solutions for velocity and temperature. The entropy generation equation is also simplified based on the same assumptions and then is converted to dimensionless form by using characteristic entropy generation. A time averaged entropy generation rate followed by a global entropy generation rate are calculated and graphically represented for further analysis and inspecting the effect of different parameters on the entropy generation.

Keywords: thermo-acoustics, entropy, second law of thermodynamics, Rott’s linear thermo-acoustic approximation

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Authors: Jung-Ho Moon, Tae Kwon Ha

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The effect of Yttrium addition on the microstructure and mechanical properties of Sn-Zn eutectic alloy, which has been attracting intensive focus as a Pb-free solder material, was investigated in this study. Phase equilibrium has been calculated by using FactSage® to evaluate the composition and fraction of equilibrium intermetallic compounds and construct a phase diagram. In the case of Sn-8.8 Zn eutectic alloy, the as-cast microstructure was typical lamellar. With addition of 0.25 wt. %Y, a large amount of pro-eutectic phases have been observed and various YZnx intermetallic compounds were expected to successively form during cooling. Hardness of Sn-8.8 Zn alloy was not affected by Y-addition and both alloys could be rolled by 90% at room temperature.

Keywords: Sn-Zn eutectic alloy, yttrium, FactSage®, microstructure, mechanical properties

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Authors: Kalyani Kulkarni, Bharat Chaudhari

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This paper addresses the issue of resource allocation in the emerging cognitive technology. Focusing the quality of service (QoS) of primary users (PU), a novel method is proposed for the resource allocation of secondary users (SU). In this paper, we propose the unique utility function in the game theoretic model of Cognitive Radio which can be maximized to increase the capacity of the cognitive radio network (CRN) and to minimize the interference scenario. The utility function is formulated to cater the need of PUs by observing Signal to Noise ratio. The existence of Nash equilibrium is for the postulated game is established.

Keywords: cognitive networks, game theory, Nash equilibrium, resource allocation

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Authors: Alexander J. Severinsky

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Radiative forces of greenhouse gases (GHG) increase the temperature of the Earth's surface, more on land, and less in oceans, due to their thermal capacities. Given this inertia, the temperature increase is delayed over time. Air temperature, however, is not delayed as air thermal capacity is much lower. In this study, through analysis and synthesis of multidisciplinary science and data, an estimate of atmospheric temperature increase is made. Then, this estimate is used to shed light on current observations of ice and snow loss, desertification and forest fires, and increased extreme air disturbances. The reason for this inquiry is due to the author’s skepticism that current changes cannot be explained by a "~1 ^oC" global average surface temperature rise within the last 50-60 years. The only other plausible cause to explore for understanding is that of atmospheric temperature rise. The study utilizes an analysis of air temperature rise from three different scientific disciplines: thermodynamics, climate science experiments, and climactic historical studies. The results coming from these diverse disciplines are nearly the same, within ± 1.6%. The direct radiative force of GHGs with a high level of scientific understanding is near 4.7 W/m² on average over the Earth’s entire surface in 2018, as compared to one in pre-Industrial time in the mid-1700s. The additional radiative force of fast feedbacks coming from various forms of water gives approximately an additional ~15 W/m². In 2018, these radiative forces heated the atmosphere by approximately 5.1 ^oC, which will create a thermal equilibrium average ground surface temperature increase of 4.6 ^oC to 4.8 ^oC by the end of this century. After 2018, the temperature will continue to rise without any additional increases in the concentration of the GHGs, primarily of carbon dioxide and methane. These findings of the radiative force of GHGs in 2018 were applied to estimates of effects on major Earth ecosystems. This additional force of nearly 20 W/m² causes an increase in ice melting by an additional rate of over 90 cm/year, green leaves temperature increase by nearly 5 ^oC, and a work energy increase of air by approximately 40 Joules/mole. This explains the observed high rates of ice melting at all altitudes and latitudes, the spread of deserts and increases in forest fires, as well as increased energy of tornadoes, typhoons, hurricanes, and extreme weather, much more plausibly than the 1.5 ^oC increase in average global surface temperature in the same time interval. Planned mitigation and adaptation measures might prove to be much more effective when directed toward the reduction of existing GHGs in the atmosphere.

Keywords: greenhouse radiative force, greenhouse air temperature, greenhouse thermodynamics, greenhouse historical, greenhouse radiative force on ice, greenhouse radiative force on plants, greenhouse radiative force in air

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Authors: R. C. Ferreira, H. H. C. De Lima, A. A. Cândido, O. M. Couto Junior, P. A. Arroyo, K. Q De Carvalho, G. F. Gauze, M. A. S. D. Barros

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Removal of the widespread used drug paracetamol from water was investigated using activated carbon originated from dende coconut mesocarp and babassu coconut mesocarp. Kinetic and equilibrium data were obtained at different values of pH. Babassu activated carbon showed higher efficiency due to its acidity and higher microporosity. Pseudo-second order model was better adjusted to the kinetic results. Equilibrium data may be represented by Langmuir equation. Lower solution pH provided better removal efficiency as the carbonil groups may be attracted by the positively charged carbon surface.

Keywords: adsorption, activated carbon, babassu, dende

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Authors: G. B. Hong

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Liquid-Liquid Equilibrium (LLE) data are measured for the ternary mixtures of water + 1-butanol + butyl acetate and quaternary mixtures of water + 1-butanol + butyl acetate + glycerol at atmospheric pressure at 313.15 K. In addition, isothermal Vapor–Liquid–Liquid Equilibrium (VLLE) data are determined experimentally at 333.15 K. The region of heterogeneity is found to increase as the hydrophilic agent (glycerol) is introduced into the aqueous mixtures. The experimental data are correlated with the NRTL model. The predicted results from the solution model with the model parameters determined from the constituent binaries are also compared with the experimental values.

Keywords: LLE, VLLE, hydrophilic agent, NRTL

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Authors: Shoji Katagiri

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This paper is to clarify the relationship between ICT and income inequality. To do so, we develop the general equilibrium model with ICT investment, obtain the equilibrium solutions, and then simulate the model with these solutions for some OECD countries. As a result, generally, during the corresponding periods we confirm that the relationship between ICT investment and income inequality is positive. In this mode, the increment of the ratio of ICT investment to the aggregated investment in stock enhances the capital’s share of income, and finally leads to income inequality such as the increase of the share of the top decile income. Although we confirm the positive relationship between ICT investment and income inequality, the upward trend for that relationship depends on the values of parameters for the making use of the simulations and these parameters are not deterministic in the magnitudes on the calculated results for the simulations.

Keywords: ICT, inequality, capital accumulation, technology

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Authors: Soo Hyung Park, Seong Beom Kim, Wontae Lee, Jin Chul Joo, Jungmin Lee, Jongsoo Choi

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A newly-developed electromagnetically vibrated solid-phase microextraction (SPME) device for extracting nonpolar organic compounds from aqueous matrices was evaluated in terms of sorption equilibrium time, precision, and detection level relative to three other more conventional extraction techniques involving SPME, viz., static, magnetic stirring, and fiber insertion/retraction. Electromagnetic vibration at 300~420 cycles/s was found to be the most efficient extraction technique in terms of reducing sorption equilibrium time and enhancing both precision and linearity. The increased efficiency for electromagnetic vibration was attributed to a greater reduction in the thickness of the stagnant-water layer that facilitated more rapid mass transport from the aqueous matrix to the SPME fiber. Electromagnetic vibration less than 500 cycles/s also did not detrimentally impact the sustainability of the extracting performance of the SPME fiber. Therefore, electromagnetically vibrated SPME may be a more powerful tool for rapid sampling and solvent-free sample preparation relative to other more conventional extraction techniques used with SPME.

Keywords: electromagnetic vibration, organic compounds, precision, solid-phase microextraction (SPME), sorption equilibrium time

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Authors: Bakur Gulua

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In this work, we consider some boundary value problems for the plate. The plate is the elastic material with voids. The state of plate equilibrium is described by the system of differential equations that is derived from three-dimensional equations of equilibrium of an elastic material with voids (Cowin-Nunziato model) by Vekua's reduction method. Its general solution is represented by means of analytic functions of a complex variable and solutions of Helmholtz equations. The problem is solved analytically by the method of the theory of functions of a complex variable.

Keywords: the elastic material with voids, boundary value problems, Vekua's reduction method, a complex variable

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Authors: Qing Dai, Zhengkui Lin, Jiajia Zhang, Yi Qu

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Based on activity method, this paper focuses on morning commuting behavior when commuters travel with autonomous vehicles (AVs). Firstly, a net utility function of commuters is constructed by the activity utility of commuters at home, in car and at workplace, and the disutility of travel time cost and that of schedule delay cost. Then, this net utility function is applied to build an equilibrium model. Finally, under the assumption of constant marginal activity utility, the properties of equilibrium are analyzed. The results show that, in autonomous driving, the starting and ending time of morning peak and the number of commuters who arrive early and late at workplace are the same as those in manual driving. In automatic driving, however, the departure rate of arriving early at workplace is higher than that of manual driving, while the departure rate of arriving late is just the opposite. In addition, compared with manual driving, the departure time of arriving at workplace on time is earlier and the number of people queuing at the bottleneck is larger in automatic driving. However, the net utility of commuters and the total net utility of system in automatic driving are greater than those in manual driving.

Keywords: autonomous cars, bottleneck model, activity utility, user equilibrium

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Authors: M. M. El-Awad

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The availability of computers and educational software nowadays helps engineering students acquire better understanding of engineering principles and their applications. With these facilities, students can perform sensitivity and optimisation analyses which were not possible in the past by using slide-rules and hand calculators. Standard textbooks in engineering thermodynamics also use software such as Engineering Equation Solver (EES) and Interactive Thermodynamics (IT) for solving calculation-intensive and design problems. Unfortunately, engineering students in most developing countries do not have access to such applications which are protected by intellectual-property rights. This paper shows how Microsoft ExcelTM and VBA (Visual Basic for Applications), which are normally distributed with personal computers and laptops, can be used as an alternative modelling platform for thermodynamic analyses and optimisation. The paper describes the VBA user-defined-functions developed for determining the refrigerants properties with Excel. For illustration, the combination is used to model and optimise the intermediate temperature for a propane/iso-butane cascade refrigeration system.

Keywords: thermodynamic optimisation, engineering education, excel, VBA, cascade refrigeration system

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Authors: F. A. Saracoglu Varol, H. Agaccıoglu

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Experimental studies to investigate the depth of the scour conducted at a side-weir intersection located at the 1800 curved flume which located Hydraulic Laboratory of Yıldız Technical University, Istanbul, Turkey. Side weirs were located at the middle of the straight part of the main channel. Three different lengths (25, 40 and 50 cm) and three different weir crest height (7, 10 and 12 cm) of the side weir placed on the side weir station. There is no scour when the material is only kaolin. Therefore, the cohesive bed was prepared by properly mixing clay material (kaolin) with 31% sand in all experiments. Following 24h consolidation time, in order to observe the effect of flow intensity on the scour depth, experiments were carried out for five different upstream Froude numbers in the range of 0.33-0.81. As a result of this study the relation between scour depth and upstream flow intensity as a function of time have been established. The longitudinal velocities decreased along the side weir; towards the downstream due to overflow over the side-weirs. At the beginning, the scour depth increases rapidly with time and then asymptotically approached constant values in all experiments for all side weir dimensions as in non-cohesive sediment. Thus, the scour depth reached equilibrium conditions. Time to equilibrium depends on the approach flow intensity and the dimensions of side weirs. For different heights of the weir crest, dimensionless scour depths increased with increasing upstream Froude number. Equilibrium scour depths which formed 7 cm side-weir crest height were obtained higher than that of the 12 cm side-weir crest height. This means when side-weir crest height increased equilibrium scour depths decreased. Although the upstream side of the scour hole is almost vertical, the downstream side of the hole is inclined.

Keywords: clay-sand mixed sediments, scour, side weir, hydraulic structures

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Authors: Umar Yusuf Batsari

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Let E be a uniformly smooth and uniformly convex real Banach space and C be a nonempty, closed and convex subset of E. Let $V= \{S_i : C\to C, ~i=1, 2, 3\cdots N\}$ be a convex set of relatively nonexpansive mappings containing identity. In this paper, an iterative sequence obtained from CQ algorithm was shown to have strongly converge to a point $\hat{x}$ which is a common fixed point of relatively nonexpansive mappings in V and also solve the system of equilibrium problems in E. The result improve some existing results in the literature.

Keywords: relatively nonexpansive mappings, strong convergence, equilibrium problems, uniformly smooth space, uniformly convex space, convex set, kadec klee property

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Authors: M. S. Mahmoud

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In this paper, the adsorption performance of a novel environmental friendly material, calcium alginate gel beads as a non-conventional technique for the successful removal of copper ions from aqueous solution are reported on. Batch equilibrium studies were carried out to evaluate the adsorption capacity and process parameters such as pH, adsorbent dosages, initial metal ion concentrations, stirring rates and contact times. It was observed that the optimum pH for maximum copper ions adsorption was at pH 5.0. For all contact times, an increase in copper ions concentration resulted in decrease in the percent of copper ions removal. Langmuir and Freundlich's isothermal models were used to describe the experimental adsorption. Adsorbent was characterization using Fourier transform-infrared (FT-IR) spectroscopy and Transmission electron microscopy (TEM).

Keywords: adsorption, alginate polymer, isothermal models, equilibrium

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Authors: Ho Yuan-Hong, Huang Chiung-Ju

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This study conducts simulation analyses to find the optimal debt ceiling of Taiwan, while factoring in welfare maximization under a dynamic stochastic general equilibrium framework. The simulation is based on Taiwan's 2001 to 2011 economic data and shows that welfare is maximized at a "debt"⁄"GDP" ratio of 0.2, increases in the "debt"⁄"GDP " ratio leads to increases in both tax and interest rates and decreases in the consumption ratio and working hours. The study results indicate that the optimal debt ceiling of Taiwan is 20% of GDP, where if the "debt"⁄"GDP" ratio is greater than 40%, the welfare will be negative and result in welfare loss.

Keywords: debt sustainability, optimal debt ceiling, dynamic stochastic general equilibrium, welfare maximization

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Authors: Abdelhak Soudani

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Using the limit equilibrium method in geotechnical field is very important for large projects. This work contributes to the understanding and analysis of the building unstable slopes by the technique of soil nailed with the used of software called GEO-SLOPE calculation based on limit equilibrium method. To achieve our objective, we began a review of the literature on landslides, and techniques of slope stability. Then, we presented a real case slope likely to slip through the realization of the EastWest Highway (M5 stretch between Khemis Miliana and Hoceinia). We also process the application of reinforcement technique nailed soil. The analysis is followed by a parametric study, which shows the impact of parameters given or chosen on various outcomes. Another method of reinforcement (use of micro-piles) has been suggested for improving the stability of the slope

Keywords: slope stability, strengthening, slip, soil nail, GEO-SLOPE

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Authors: Rihana Hadjeb, Djamel Barkat

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Schiff bases derived from o-hydroxybenzaldehyde has attracted a great interest not only for its promising applications towards linear and non-linear optical properties, biological activity and technological applications but also used as model compounds for the theory of hydrogen bonding. Due to its intramolecular hydrogen bonding, depending on the position of proton in the hydrogen bond o-hydroxy salicylidene Schiff bases exhibit two tautomeric forms, enol-imine (E-form) and keto-enamine (K-form) both in solution and in crystalline state. A zwitterionic structure also appears due to a proton transfer in enol – imine and keto – amine tautomer. These classes of compounds also exhibit thermochromic and photochromic behavior. We undertook in this study the synthesis of ten compounds of hydroxy Schiff bases from the condensation of salicylic aldehyde and aniline substituted in the ortho, meta and para by the methyl, chloro and nitro groups. To study the keto-enol equilibrium of the compounds; UV-VIS spectra were studied in different polarity solvents. The compounds were in tautomeric equilibrium (enol imine O–H•••N, keto-amine O•••H–N forms). For some derivatives of salicylideneanilines the keto-amine form was observed in both ethanol and dioxane. IR results showed that all Schiff bases studied favor the enol-imine form over the keto form.

Keywords: salicylideneaniline, tautomerism, keto-enol equilibrium, UV-VIS spectroscopy, solvent effect

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Authors: Kumar N., Verma S., Park J., Srivastava V. C.

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Organic carbonates have the potential to be used as fuels and because of this, their production through non-phosgene routes is a thrust area of research. Di-ethyl carbonate (DEC) synthesis from propylene carbonate (PC) in the presence of alcohol is a green route. In this study, the use of reduced graphene oxide (rGO) based metal oxide catalysts [rGO-MO, where M = Ce] with different amounts of graphene oxide (0.2%, 0.5%, 1%, and 2%) has been investigated for the synthesis of DEC by using PC and ethanol as reactants. The GO sheets were synthesized by an electrochemical process and the catalysts were synthesized using an in-situ method. A theoretical study of the thermodynamics of the reaction was done, which revealed that the reaction is mildly endothermic. The theoretical value of optimum temperature was found to be 420 K. The synthesized catalysts were characterized for their morphological, structural and textural properties using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), N2 adsorption/desorption, thermogravimetric analysis (TGA), and Raman spectroscopy. Optimization studies were carried out to study the effect of different reaction conditions like temperature (140 °C to 180 °C) and catalyst dosage (0.102 g to 0.255 g) on the yield of DEC. Amongst the various synthesized catalysts, 1% rGO-CeO2 gave the maximum yield of DEC.

Keywords: GO, DEC, propylene carbonate, transesterification, thermodynamics

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Authors: Mostafa Rajabi, Kazem Mahanpoor

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Performances of the methyl red (MR) dye adsorption on poly(methyl methacrylate)/graphene oxide (PMMA/GO) and poly(methyl methacrylate)/graphene oxide-Fe3O4 (PMMA/GO-Fe3O4) nanocomposites as adsorbents were investigated. Our results showed that for adsorption of MR dye on PMMA/GO-Fe3O4 and PMMA/GO nanocomposites, 80 minutes, 298 K, and pH 2 were the best contact time, temperature and pH value for process, respectively, because the optimum adsorption of the MR dye with both nanocomposite adsorbents were observed in these values of the parameters. The equilibrium study results showed that PMMA/GO-Fe3O4 and PMMA/GO were suitable adsorbents for MR dye removing and were best in agreement with the Langmuir isotherm model.

Keywords: adsorption, isotherm, methyl methacrylate, methyl red, nanocomposite, nano magnetic Fe3O4

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Authors: M. Unis, S. Turky, A. Elalem, A. Meshrghi

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The Esterification kinetics of acetic acid with isopropnol in the presence of sulfuric acid as a homogenous catalyst was studied with isothermal batch experiments at 60,70 and 80°C and at a different molar ratio of isopropnol to acetic acid. Investigation of kinetics of the reaction indicated that the low of molar ratio is favored for esterification reaction, this is due to the reaction is catalyzed by acid. The maximum conversion, approximately 60.6% was obtained at 80°C for molar ratio of 1:3 acid : alcohol. It was found that increasing temperature of the reaction, increases the rate constant and conversion at a certain mole ratio, that is due to the esterification is exothermic. The homogenous reaction has been described with simple power-law model. The chemical equilibrium combustion calculated from the kinetic model in agreement with the measured chemical equilibrium.

Keywords: artificial flavors, esterification, chemical equilibria, isothermal

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Authors: Said M. AL-Mashaikhi, El-Said I. El-Shafey, Fakhreldin O. Suliman, Saleh Al-Busafi

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Activated carbon (AC) was prepared from date palm leaflets via NaOH activation. AC was oxidized using nitric acid, producing oxidized activated carbon (OAC). OAC was surface functionalized using different amine surfactants, including methylamine (ONM), ethylamine (ONE), and diethylamine (ONDE) using the amide coupling process. Produced carbons were surface characterized for surface area and porosity, X-ray diffraction, SEM, FTIR, and TGA. AC surface area (580 m²/g) has shown a decrease in oxidation to 260 m²/g for OAC. On amine functionalization, the surface area has further decreased to 218, 108, and 20 m²/g on functionalization with methylamine, ethylamine, and diethylamine, respectively. FTIR and TGA showed that the nature of amine functionalization of AC is chemical. Methylene blue sorption was tested on these carbons in terms of kinetics and equilibrium. Sorption was found faster on amine-functionalized carbons than both AC and OAC, and this is due to hydrophobic interaction with the alkyl groups immobilized with data following pseudo second-order reaction. On the other hand, AC showed the slowest adsorption kinetic process due to the diffusion in the porous structure of AC. Sorption equilibrium data was found to follow the Langmuir sorption isotherm with maximum sorption found on ONE. Regardless of its lower surface area than activated carbon, ethylamine functionalized AC showed better performance than AC in terms of kinetics and equilibrium for dye removal.

Keywords: activated carbon, dye removal, functionalization, hydrophobic interaction, water treatment

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Authors: Amokrane Boufares, Elise Provost, Veronique Osswald, Pascal Clain, Anthony Delahaye, Laurence Fournaison, Didier Dalmazzone

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Gas hydrates have long been considered as problematic for flow assurance in natural gas and oil transportation. On the other hand, they are now seen as future promising materials for various applications (i.e. desalination of seawater, natural gas and hydrogen storage, gas sequestration, gas combustion separation and cold storage and transport). Nonetheless, a better understanding of the crystallization mechanism of gas hydrate and of their formation kinetics is still needed for a better comprehension and control of the process. To that purpose, measuring the real-time evolution of the dissolved gas concentration in the aqueous phase during hydrate formation is required. In this work, CO₂ hydrates were formed in a stirred reactor equipped with an Attenuated Total Reflection (ATR) probe coupled to a Fourier Transform InfraRed (FTIR) spectroscopy analyzer. A method was first developed to continuously measure in-situ the CO₂ concentration in the liquid phase during solubilization, supersaturation, hydrate crystallization and dissociation steps. Thereafter, the measured concentration data were compared with those of equilibrium concentrations. It was observed that the equilibrium is instantly reached in the liquid phase due to the fast consumption of dissolved gas by the hydrate crystallization. Consequently, it was shown that hydrate crystallization kinetics is limited by the gas transfer at the gas-liquid interface. Finally, we noticed that the liquid-hydrate equilibrium during the hydrate crystallization is governed by the temperature of the experiment under the tested conditions.

Keywords: gas hydrate, dissolved gas, crystallization, infrared spectroscopy

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Authors: Shahbaa F. Bdewi, Bakhtyar K. Aziz, Ayad A. R. Mutar

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Nano-materials show different surface properties due to their high surface area and active sites. This study investigates the feasibility of using nano-MgO (NMO) for removing Congo red (CR) dye from wastewater. NMO was prepared by molten salt method. Equilibrium experiments show the equilibrium was reached after 120 minutes and maximum adsorption efficiency was obtained in acidic media up to pH 6. Isotherm studies revealed the favorability of the adsorption process. The overall adsorption process was spontaneous and endothermic in nature with a maximum adsorption capacity of 1100 mg g-1 at 40°C as estimated from Langmuir isotherm. The adsorption kinetics was found to follow pseudo second-order rate equation. Relatively high activation energy (180.7 kJ mol-1) was obtained which is consistent with chemisorption mechanism for the adsorption process.

Keywords: adsorption, congo red, magnesium oxide, nanoparticles

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Authors: Yu-Shan Hsu

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This paper studies a two-sector growth model with a technology of social constant returns and with a utility that features either a zero or a positive income effect on the demand for leisure. The purpose is to investigate how the existence of aggregate instability or equilibrium indeterminacy depends on both the intensity of the income effect on the demand for leisure and the value of the labor supply elasticity. The main finding is that when there is a factor intensity reversal between the private perspective and the social perspective, indeterminacy arises even if the utility has a positive income effect on leisure demand. Moreover, we find that a smaller value of the labor supply elasticity increases the range of the income effect on leisure demand and thus increases the possibility of equilibrium indeterminacy. JEL classification: E3; O41

Keywords: indeterminacy, non-separable preferences, income effect, labor supply elasticity

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Authors: Ellis D. Cooper

Abstract:

“Circularchy” is supposed to be an adjustable formal framework with enough expressive power to articulate biological theory about Earthly Life in the sense of multi-scale biological autonomy constrained by non-equilibrium thermodynamics. “Formal framework” means specifically a multi-sorted first-order-theorywithequality (for each sort). Philosophically, such a theory is one kind of “microlect,” which means a “way of speaking” (or, more generally, a “way of behaving”) for overtly expressing a “mental model” of some “referent.” Other kinds of microlect include “natural microlect,” “diagrammatic microlect,” and “behavioral microlect,” with examples such as “political theory,” “Euclidean geometry,” and “dance choreography,” respectively. These are all describable in terms of a vocabulary conforming to grammar. As aspects of human culture, they are possibly reminiscent of Ernst Cassirer’s idea of “symbolic form;” as vocabularies, they are akin to Richard Rorty’s idea of “final vocabulary” for expressing a mental model of one’s life. A formal microlect is presented by stipulating sorts, variables, calculations, predicates, and postulates. Calculations (a.k.a., “terms”) may be composed to form more complicated calculations; predicates (a.k.a., “relations”) may be logically combined to form more complicated predicates; and statements (a.k.a., “sentences”) are grammatically correct expressions which are true or false. Conclusions are statements derived using logical rules of deduction from postulates, other assumed statements, or previously derived conclusions. A circularchy is a formal microlect constituted by two or more sub-microlects, each with its distinct stipulations of sorts, variables, calculations, predicates, and postulates. Within a sub-microlect some postulates or conclusions are equations which are statements that declare equality of specified calculations. An equational bond between an equation in one sub-microlect and an equation in either the same sub-microlect or in another sub-microlect is a predicate that declares equality of symbols occurring in a side of one equation with symbols occurring in a side of the other equation. Briefly, a circularchy is a network of equational bonds between sub-microlects. A circularchy is solvable if there exist solutions for all equations that satisfy all equational bonds. If a circularchy is not solvable, then a challenge would be to discover the obstruction to solvability and then conjecture what adjustments might remove the obstruction. Adjustment means changes in stipulated ingredients (sorts, etc.) of sub-microlects, or changes in equational bonds between sub-microlects, or introduction of new sub-microlects and new equational bonds. A circularchy is modular insofar as each sub-microlect is a node in a network of equation bonds. Solvability of a circularchy may be conjectured. Efforts to prove solvability may be thwarted by a counter-example or may lead to the construction of a solution. An automated theorem-proof assistant would likely be necessary for investigating a substantial circularchy, such as one purported to represent Earthly Life. Such investigations (chains of statements) would be concurrent with and no substitute for simulations (chains of numbers).

Keywords: autonomy, first-order theory, mathematics, thermodynamics

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